The invention relates to the use of derivatives of quinoline- or quinoxaline-5,8-diones or -diols in cosmetics, especially for the dyeing of keratinous matter and, in particular, the hair. It also relates to novel compounds of this class. The invention is also directed to dyeing compositions comprising the said compounds and to the method of dyeing keratinous fibres.
In the literature, adducts of pyrrole compounds and N,N-dialkylarylamines or N-alkylarylamines with quinoline-5,8-diones are known.
Thus J. Griffiths and C. Blackburn, in the journal J. Chem. Res. (S), 1982, pages 320-321, the disclosure of which is incorporated by reference herein, studied the reactions of 1,4-naphthoquinone and its derivatives with N,N-dialkylarylamines.
In the articles by K. Yoshida et al., Bull. Chem. Soc. Jpn., 1988, 61, pages 4335-4340, and Chem. Lett., 1987, pages 1191-1194, the disclosures of each which are incorporated by reference herein, it was shown that, in the absence of metal salts, the reaction of quinoline-5,8-dione with N,N-dialkylarylamines was slow and led to isomer mixtures of 6- and 7-[p-(dialkylamino)phenyl]quinoline-5,8-dione whereas, in the presence of metal salts, only the compounds arylated in position 6 were obtained. The reactions are generally conducted in acetic acid; in certain cases, a chloroform-ethanol/HCl mixture can also be used, according to the article by K. Yoshida et al. in Chem. Lett., 1991, 2027-2030, the disclosure of which is incorporated by reference herein.
K. Yoshida et al. in J. Chem. Soc. Perkin Trans. I, 1992, 2713-2715, the disclosure of which is incorporated by reference herein, also studied the dioxo-5,8-quinolylpyrroles for their physiological properties and their colouring properties on an unspecified substrate. Furthermore, in the journal J. Chem. Soc. Perkin Trans. I, 1994, pages 2521-2523, the disclosure of which is incorporated by reference herein, K. Yoshida et al. took an interest in quinoline-5,8-diones carrying a substituent in position 6, for the purpose of a utility as a precursor of dyes which can be used in optoelectronics.
Furthermore, the only known derivative of quinoxaline corresponds to the following formula: 
In accordance with the above text, adducts of pyrrole compounds and N,N-dialkylarylamines or N-alkylarylamines with quinoline-5,8-diones are already known, but no allusion whatsoever is made as regards their application in cosmetics.
On the other hand, the addition compounds of indoles with quinolinediones or quinoxalines are novel.
In the field of hair dyeing, dyes are sought which are reproducible, with rich and varied shades, thereby making it possible to obtain a wide pallet of colours capable of satisfying the formulator.
The inventors have now discovered that a new class of derivatives of quinoline- or quinoxaline-5,8-diones or -diols can be used for the dyeing of keratinous matter and, in particular, the hair. This new class, which is the subject of the invention, satisfies the above-described objectives and, moreover, is highly accessible, since the majority of these dyes are prepared in a single stage which is easy to implement.
The dyeings obtained with the aid of these dyes can exhibit reproducible, intensive and varied shades.
The present invention therefore provides for the use of compounds of general formulae (I) and (II) defined below in the dyeing of keratinous matter and, in particular, of the hair.
The present invention also provides novel compounds of this class.
The invention additionally provides dyeing compositions and a method of dyeing which employs them.
Other features, aspects and advantages of the invention will appear more clearly still on reading the description and various examples which follow.
One subject of the present invention is the use in the dyeing of keratinous matter and, in particular, of the hair of compounds of general formulae (I) and (II): 
in which:
Q represents the groups 
X represents the group CH or a nitrogen atom;
T represents a hydrogen atom, a halogen atom or a hydroxyl group;
R1, R2, R3, R4 and R5, which are identical or different, are selected from a hydrogen atom, C1-C4 alkoxy groups, amino groups xe2x80x94N(W1)(W2), groups xe2x80x94NHxe2x80x94COxe2x80x94W1, groups xe2x80x94Oxe2x80x94COxe2x80x94W1, a hydroxyl group, a carboxylic acid group, derivatives of a carboxylic acid group, such as esters, amides, mineral salts, and organic amine salts, halogen atoms, linear and branched C1-C4 alkyl groups optionally substituted by a substituent selected from nitrile groups, a carboxylic acid group, derivatives of a carboxylic acid group, such as esters, amides, mineral salts, and organic amine salts, a hydroxyl group, groups such as: 
ether groups xe2x80x94OSi(W1)3, amino groups 
xe2x80x83and amido groups 
xe2x80x83or 
Z is selected from a hydrogen atom, a benzyl group, a phenyl group optionally substituted by a substituent selected from a hydroxyl group, groups xe2x80x94Oxe2x80x94COxe2x80x94W1, amino groups xe2x80x94N(W1)(W2), groups xe2x80x94NHxe2x80x94COxe2x80x94W1 and a nitrile group; linear and branched C1-C8 alkyl groups optionally substituted by a substituent selected from a nitrile group, a carboxylic acid group, derivatives of a carboxylic acid group, such as esters, amides, mineral salts, and organic amine salts, a hydroxyl group, groups such as: 
xe2x80x83ether groups xe2x80x94OSi(W1)3, amino groups 
xe2x80x83and amido groups 
xe2x80x83or 
W1 and W2, which are identical or different, are selected from a hydrogen atom and linear and branched C1-C4 alkyl groups,
W3 and W4, which are identical or different, are selected from a hydrogen atom and linear and branched C1-C4 alkyl groups optionally substituted by at least one substituent selected from a hydroxyl group, groups xe2x80x94COxe2x80x94Oxe2x80x94W1, groups xe2x80x94Oxe2x80x94COxe2x80x94W1, and amino groups xe2x80x94N(W1)(W2).
The C1-C4 alkyl groups or the C1-C4 alkyl moieties of alkoxy groups can be linear or branched and are selected in particular from the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, preferably from the groups methyl, ethyl and n-butyl.
The C1-C8 alkyl groups can be linear or branched; they can be substituted by a nitrile group, a carboxylic acid group or its derivatives such as esters, amides, mineral salts and organic amine salts, a hydroxyl group, an ester group such as alkoxycarbonyl, carboxyl, alkylcarbonyloxy, formyloxy, tosyloxy, an amino group, an amido group such as aminocarbonyl or acetamido, or an ether group selected from trialkylsiloxy and siloxy groups.
These C1-C8 alkyl groups are selected in particular from the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl and octyl, and preferably from the groups methyl and pentyl.
The halogen atoms are selected from chlorine, bromine, fluorine and iodine, and in particular chlorine.
Among the compounds of formulae (I) and (II) defined above, mention may be made in particular of the following compounds:
6-(1-pentyl-1H-pyrrol-2-yl)quinoline-5,8-dione,
6-(1-benzyl-1H-pyrrol-2-yl)quinoline-5,8-dione,
methyl 4-(5,8-dioxo-5,8-dihydroquinolin-6-yl)-2,5-dimethyl-1H-pyrrole-3-carboxylate,
N-[2-[2-(5,8-dioxo-5,8-dihydroquinolin-6-yl)pyrrol-1-yl]ethyl]acetamide,
6-(1-phenyl-1H-pyrrol-2-yl)quinoline-5,8-dione,
3-[2-(5,8-dioxo-5,8-dihydroquinolin-6-yl)pyrrol-1-yl]propionitrile,
6-chloro-7-(1-methyl-1H-pyrrol-2-yl)quinoline-5,8-dione,
6-(1,2-dimethyl-1H-indol-3-yl)quinoline-5,8-dione,
6-(1-benzyl-1H-indol-3-yl)quinoline-5,8-dione,
6-(2-phenyl-1H-indol-3-yl)quinoline-5,8-dione,
6-(2-methyl-1H-indol-3-yl)quinoline-5,8-dione,
6-(2-methyl-1H-indol-3-yl)quinoline-5,8-dione,
6-[p-(N,N-(2-diacetyloxyethyl)amino)phenyl]-quinoline-5,8-dione,
6-(1-methyl-1H-pyrrol-2-yl)quinoxaline-5,8-dione,
6-(1-methyl-1H-pyrrol-2-yl)quinoline-5,8-dione,
7-(1-methyl-1H-pyrrol-2-yl)quinoline-5,8-dione,
6-[p-(N,N-diethylamino)phenyl]quinoline-5,8-dione,
6-[p-(N,N-dimethylamino)phenyl]quinoline-5,8-dione
7-[p-(N,N-dimethylamino)phenyl]quinoline-5,8-dione
6-[4-(N,N-diethylamino)-3-isopropenylphenyl]-quinoline-5,8-dione,
6-[4-(N,N-diethylamino)-3-(N-acetylamino)phenyl]quinoline-5,8-dione,
6-[4-(N, N-dimethylamino)-3-isopropenylphenyl]-quinoline-5,8-dione,
6-[4-(N,N-di-n-butylamino)-3-hydroxyphenyl]-quinoline-5,8-dione,
6-[p-(N-n-butylamino)phenyl]quinoline-5,8-dione,
6-[p-(N-methylamino)phenyl]quinoline-5,8-dione,
6-(1-methyl-1H-pyrrol-2-yl)quinoline-5,8-diol,
7-(1-methyl-1H-pyrrol-2-yl)quinoline-5,8-diol.
Among the compounds of formulae (I) and (II) which can be used in the present invention, more particular preference is given to the derivatives of formula (I) or (II) for which X represents CH; T represents H; Q is selected from: 
R1 represents H or xe2x80x94OH; R2, R3, R4 and R5 each represent H; Z represents H or CH3, phenyl, benzyl or 2-cyanoethyl; and W3 and W4 are selected from H and the groups methyl, ethyl and n-butyl.
The novel compounds correspond to the formulae (I) and (II) of the invention, with the proviso that:
when Q represents 
X=C and T=H, then Z is other than the methyl group;
when Q represents 
and one of the substituents W3 and W4 represents a hydrogen atom, the other substituent does not represent a methyl or n-butyl group; and
when Q represents 
and the substituents W3 and W4 are identical, they do not represent either a methyl group or an ethyl group.
These compounds can be defined by the general formulae (III) and (IV): 
in which Q represents 
X represents the group CH or a nitrogen atom;
T represents a hydrogen atom, a halogen atom or a hydroxyl group;
R1, R2, R3, R4 and R5, which are identical or different, are selected from a hydrogen atom, C1-C4 alkoxy groups, amino groups xe2x80x94N(W1)(W2), groups xe2x80x94NHxe2x80x94COxe2x80x94W1, groups xe2x80x94Oxe2x80x94COxe2x80x94W1, a hydroxyl group, a carboxylic acid group, derivatives of a carboxylic acid group, such as esters, amides, mineral salts, and organic amine salts, halogen atoms, linear and branched C1-C4 alkyl groups optionally substituted by a substituent selected from a nitrile group, a carboxylic acid group, derivatives of a carboxylic acid group, such as esters, amides, mineral salts and organic amine salts, a hydroxyl group, groups such as: 
xe2x80x83ether groups xe2x80x94OSi(W1)3, amino groups 
xe2x80x83amido groups 
Z2 represents a hydrogen atom, a benzyl group, a phenyl group optionally substituted by a substituent selected from a hydroxyl group, groups xe2x80x94COxe2x80x94Oxe2x80x94W1, groups xe2x80x94Oxe2x80x94COxe2x80x94W1, amino groups xe2x80x94N(W1)(W2), amino groups xe2x80x94COxe2x80x94N(W1)(W2), amino groups xe2x80x94NHxe2x80x94COxe2x80x94W1 and a nitrile group; linear and branched C1-C8 alkyl groups optionally substituted by a substituent selected from a nitrile group, a carboxylic acid group, derivatives of a carboxylic acid group, such as esters, amides, mineral salts, and organic amine salts, a hydroxyl group, groups such as: 
xe2x80x83ether groups xe2x80x94OSi(W1)3, amino groups 
xe2x80x83amido groups 
xe2x80x83or 
Z1 has the same meanings as Z2 with the proviso that Z1 is not methyl in the cases where T=H and X=CH,
W1 and W2, which are identical or different, are selected from a hydrogen atom and linear and branched C1-C4 alkyl groups,
W4 is selected from a hydrogen atom and linear and branched C1-C4 alkyl groups, optionally substituted by at least one substituent selected from a hydroxyl group, groups xe2x80x94COxe2x80x94Oxe2x80x94W1, groups xe2x80x94Oxe2x80x94COxe2x80x94W1, and amino groups xe2x80x94N(W1)(W2), and
W3 has the same meanings as W4 with the proviso that, when one of the substituents W3 and W4 represents a hydrogen atom, the other substituent does not represent a methyl or n-butyl group; and, when the substituents W3 and W4 are identical, they do not represent either a methyl group or an ethyl group.
Among the novel compounds of formulae (III) and (IV) defined above, mention may be made in particular of the following compounds:
6-(1-pentyl-1H-pyrrol-2-yl)quinoline-5,8-dione,
6-(1-benzyl-1H-pyrrol-2-yl)quinoline-5,8-dione,
methyl 4-(5,8-dioxo-5,8-dihydroquinolin-6-yl)-2,5-dimethyl-1H-pyrrole-3-carboxylate,
N-[2-[2-(5,8-dioxo-5,8-dihydroquinolin-6-yl)pyrrol-1-yl]ethyl]acetamide,
6-(1-phenyl-1H-pyrrol-2-yl)quinoline-5,8-dione,
3-[2-(5,8-dioxo-5,8-dihydroquinolin-6-yl)pyrrol-1-yl]propionitrile,
6-chloro-7-(1-methyl-1H-pyrrol-2-yl)quinoline-5,8-dione,
6-(1,2-dimethyl-1H-indol-3-yl)quinoline-5,8-dione,
6-(1-benzyl-1H-indol-3-yl)quinoline-5,8-dione,
6-[p-(N,N-(2-diacetyloxyethyl)amino)phenyl]-quinoline-5,8-dione,
6-(2-phenyl-1H-indol-3-yl)quinoline-5,8-dione,
6-(1-methyl-1H-indol-3-yl)quinoline-5,8-dione,
6-(2-methyl-1H-indol-3-yl)quinoline-5,8-dione,
6-(1-methyl-1H-pyrrol-2-yl)quinoxaline-5,8-dione.
Among the compounds of formulae (III) and (IV) which can be used in the present invention, more particular preference is given to the derivatives of formula (III) or (IV) in which X represents CH or N; T represents H; Q is selected from: 
R1 is selected from H and the xe2x80x94CH3 group; R2 represents H or the group xe2x80x94COOxe2x80x94W1, R3 represents H or the methyl group, R4 and R5 each represent H; W1 represents the xe2x80x94CH3 group; Z1 represents xe2x80x94C5H11, xe2x80x94(CH2)2xe2x80x94NHxe2x80x94COCH3, xe2x80x94(CH2)2xe2x80x94CN or phenyl; Z2 represents H or the xe2x80x94CH3 and benzyl groups; and W3 and W4 can represent the group xe2x80x94(CH2)2OCOW1.
The inventors have discovered that it is possible to dye keratinous fibres and, in particular, the hair by virtue of the compounds of formulae I and II. The colours obtained depend on the nature of the substituents Q and T that are used for carrying out the synthesis. By varying the nature of these substituents it is possible to produce a range of varied colours.
In accordance with the invention, the compounds of formula (I) or (II) are used for the direct dyeing, also known as semi-permanent colouring, of keratinous fibres and, in particular, the hair.
The compounds of formula (I) or (II) can be introduced as direct dyes into oxidation dyeing compositions to enrich with glints the dyeings obtained by means of the oxidation dye precursors and, optionally, of the couplers which are generally used in this type of dyeing.
The compounds of formula (II) are capable of being oxidized by atmospheric oxygen and are used for the dyeing of keratinous fibres, in particular the hair, in accordance with the method known as progressive dyeing, which comprises applying the compound of formula (II) to the fibres, in leaving it in the air generally for from 5 to approximately 45 minutes and, preferably, from 5 to approximately 30 minutes, on the said fibres, and in repeating this operation the desired number of times until, preferably, the desired coloration is obtained.
The invention also provides a dyeing composition, in particular a cosmetic dyeing composition, for keratinous matter and, in particular, for human keratinous fibres, which comprises, in a medium appropriate for dyeing, an effective amount of at least one of the compounds of formula (I) or (II) defined above.
For the purposes of the invention, the term keratinous matter refers principally to natural textile fibres such as wool and animal fur, the term human keratinous matter refers to the skin and nails, and the term human keratinous fibres refers to the hair, the eyebrows and the eyelashes. The invention is directed still more particularly to the hair of the head.
The compounds of formula (I) or (II) are generally present in proportions of between approximately 0.01 and 10%, inclusive, preferably between approximately 0.05 and 5%, inclusive, by weight, relative to the total weight of the dyeing composition.
The cosmetically acceptable medium is preferably a medium comprising water and/or organic solvents which are acceptable from the standpoint of cosmetology if the composition is intended for use in cosmetics, and, more particularly, alcohols (ethyl alcohol, isopropyl alcohol, benzyl alcohol), glycols or glycol ethers (propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol and diethylene glycol alkyl ethers, such as, for example, diethylene glycol monoethyl ether or monobutyl ether, and ethylene glycol monomethyl, monoethyl and monobutyl ethers) in concentrations of generally between 0.5 and 25%, inclusive, preferably, between approximately 2 and 15%, inclusive, by weight relative to the total weight of the composition. The cosmetically acceptable medium may also include fats such as oils and waxes.
Fatty amides, such as mono- and diethanolamides and acids derived from copra, lauric acid or oleic acid, may also be added to the composition according to the invention, in concentrations of between approximately 0.05 and 10%, inclusive, by weight.
In order to obtain varied shades, the dyeing composition according to the invention may also include, in addition to the dyes of formula (I) or (II), one or more other direct dyes which are conventionally used, and in particular nitro-functional benzenic dyes, such as nitrophenylenediamines, nitrodiphenylamines, nitroanilines, nitro-functional phenol ethers or nitrophenols, nitropyridines, anthraquinone dyes, monoazo or disazo dyes, triarylmethane dyes, azine dyes, acridine dyes and xanthene dyes, or else metallic dyes. The proportion of all these other direct dyes of addition can vary between 0.05 and 10%, inclusive, by weight relative to the total weight of the dyeing composition.
The said dyeing composition may additionally comprise any other adjuvant which is used commonly in the dyeing of keratinous matter, and, for example, surfactants which are well known in the prior art and are of anionic, cationic, nonionic, amphoteric or zwitterionic type, or mixtures thereof, thickeners, antioxidants, perfumes, sequestrants, dispersants, conditioning agents, preservatives, opacifiers, etc.
The person skilled in the art will of course take care to select the above-mentioned complementary compound or compounds such that the advantageous properties intrinsic to the dyeing composition according to the invention are not, or not substantially, adversely affected by the intended addition or additions.
The dyeing composition according to the invention can be formulated at an acidic, neutral or alkaline pH, it being possible for the pH to vary, for example, from 2 to 11 and, preferably, from 2.5 to 10, and to be adjusted by means of basifying or acidifying agents which are well known in the prior art.
Among the basifying agents, mention may be made, by way of example, of aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium hydroxide or potassium hydroxide, and the compounds of the following formula: 
in which R represents a propylene group which is optionally substituted by a hydroxyl group or a C1-C4 alkyl group; and R6, R7, R8 and R9, which are identical or different, are selected from a hydrogen atom, C1-C4 alkyl groups and C1-C4 hydroxyalkyl groups.
The acidifying agents which are used are conventionally known. Mention may be made, by way of example, of mineral acids or organic acids, such as hydrochloric acid, ortho-phosphoric acid, carboxylic acids such as tartaric acid, citric acid or lactic acid, and sulphonic acids.
When the composition is intended to be applied to human keratinous fibres, it can be presented in various forms, such as in the form of a liquid, cream or gel or any other form appropriate for carrying out the dyeing of keratinous fibres. In particular, it can be packaged under pressure in an aerosol can in the presence of a propellent, and can form a foam.
Another subject of the present invention relates to a method of dyeing human keratinous fibres and, more particularly, the hair by direct dyeing, which comprises leaving a dyeing composition comprising at least one compound of formula (I) or (II) to act on wet or dry keratinous fibres. The composition according to the invention can be used as a non-rinse composition; in other words, following application of the composition to the fibres, drying is carried out without rinsing beforehand. In the other modes of application, the composition is left to act on the fibres for a period generally varying between 3 and 60 minutes, inclusive, approximately, preferably between 5 and 45 minutes, inclusive, and the fibres are rinsed, optionally washed and rinsed again, and then dried.
An additional subject of the present invention relates to a method of progressive dyeing which comprises applying a dyeing composition comprising a compound of formula (II) defined above to the keratinous fibres, leaving the said composition in air for generally 5 to approximately 45 minutes and, preferably, from 5 to approximately 30 minutes, and then rinsing the fibres, optionally washing them, then rinsing them again, and then drying them.
By way of illustration and without any limitative character whatsoever, a number of examples will now be given of the preparation of compounds of formula (I) or (II) according to the invention, along with specific examples of dyeing compositions based on such compounds.
In order to prepare the compounds of formulae (I) to (IV), use is made generally of the procedure described by K. Yoshida, Y. Ueno, M. Suzuki, Y. Yoshida and Y. Kubo in J. Chem. Soc. Perkin Trans. I, 1992, 2713-2715, the disclosure of which is incorporated by reference herein, by reaction of quinoline-5,8-dione with a pyrrole derivative, selecting an appropriate molar ratio between the two reactants in solvent medium.